Non-foil barrier laminates

ABSTRACT

A non-foil laminate for an extended long life juice, punch or beverage container, which can be hot filled or cold filled and provides an effective barrier to oxygen ingress, for the containment of flavors and aroma and prevents the loss of Vitamin C by virtue of its reduced permeability to oxygen is provided. The laminate comprises an inner barrier layer sandwich of polyamide/EVOH/polyamide, layers of polyolefin on both the matte side (interior) and the gloss side (exterior) of the laminate and a second barrier layer of EVOH closer to the product contact surface which is not in contact with the polyamide/EVOH/polyamide sandwich or layer of polyolefin on the matte (interior) side of the laminate.

[0001] Related Applications

[0002] This application relates to Ser. No. 10/288,841 which is acontinuation-in-part of application Ser. No. 10/105,713 filed Mar. 25,2002.

FIELD OF THE INVENTION

[0003] The present invention relates to paperboard laminates and moreparticularly to non-foil paperboard laminates useful for makingcontainers for products such as fruit and citrus juices and otherbeverages, as well as non-liquid dry products, wherein the laminate hasgood barrier characteristics including the ability to prevent thetransmission of oxygen which leads to the loss of Vitamin C,aroma/flavor components and other ingredients of fruit and citrus juicesand other beverages packaged therein. The laminates also are effectivein minimizing microbial growth by virtue of their reduced permeabilityto oxygen. More particularly, this invention relates to such non-foilbarrier laminates intended for making containers known in the trade as“gable top” containers or other cartons to be used for products that areconventionally hot filled such as fruit juices or punches. Such filledcartons are stored at ambient conditions for a shelf life of 3-6 monthsbefore product quality is compromised.

BACKGROUND OF THE INVENTION

[0004] Paperboard coated with low-density polyethylene (LDPE) has beenused to make beverage containers, but falls short in providing anacceptable container for some products such as fruit juices. Inparticular, paperboard coated with LDPE has a relatively highpermeability to oxygen which may lead to loss of flavor components andvitamins through oxidation during storage. Flavor loss can also occur asa result of migration or uptake of flavor components into the LDPElayer, a process referred to as “scalping.”

[0005] The oxidative loss of vitamins and in particular Vitamin C can besubstantially reduced by the use of a laminate containing a metal foilas an oxygen barrier liner along the interior of the container. However,the economics involved in using a metal foil often require a pricepremium that limits profitability. Further, metal foil laminates areprone to develop pin holes, seriously affecting their ability to containliquids. A search for economical alternatives to foil has resulted inthe development of laminate structures utilizing coextruded polymermaterials such as polyethylene terephthalate (PET), polyvinyl chlorides,polyvinylidene chloride (PVdC) and ethylene vinyl alcohol copolymer(EVOH) as the barrier material and in particular EVOH (to provideprotection against the transfer of oxygen and aid in retention ofascorbic acid and d-limonene in citrus juice).

[0006] In addition to being less expensive than foil-containingstructures, paperboard laminates containing such barrier materials mayexhibit superior flavor retention properties due to the use of lowerlevels of LDPE as the product contact layer. Many conventionalcommercial structures for a paperboard carton for juice, punch andsimilar products now utilize a laminate containing ethylene vinylalcohol copolymer as a barrier to oxygen and to prevent flavor andvitamin loss.

[0007] Nylon has also been proposed and used commercially as a barrierpolymer in a paperboard container. It has been found not only to providean effective barrier to oxygen but also to provide thermal resistance,mechanical strength and durability. As such, it serves as anabuse-resistant layer in the construction of laminates.

[0008] In order to ensure adequate or extended shelf life duringstorage, distribution and retail display under high as well as lowhumidity conditions, i.e., to provide a laminate with good oxygenbarrier properties at relatively high humidity where EVOH is especiallysusceptible to degradation in barrier properties as a result of thepresence of moisture, the combination of nylon and EVOH has beenproposed as nylon has good barrier properties even at higher humidityconditions. Whereas nylon alone offers unacceptable barrier properties,the combination with EVOH achieves improved barrier properties of thelaminates.

[0009] As can be appreciated, considerable effort has been devoted tofinding the best layer structure in a barrier laminate for a juice,punch or other beverage carton. Thus other laminate structures utilizingcoextruded polymer material such as polypropylene, polyethyleneterephthalates, polyvinyl chlorides, polyvinylidene chloride, ethylenevinyl alcohol, and other polymeric materials as the barrier material toprovide protection against the transfer of oxygen have also beenproposed.

[0010] It is an object of the present invention to provide an improved,heat-sealable laminate material for a beverage carton which does nottransmit flavor/odor ingredients of citrus and other juices and punches,exhibits a substantial oxygen barrier, decreases substantially the lossof Vitamin C, flavor, and aroma, minimizes microbial growth, hasperformance equal to or better than that of conventionally-used polymerbarrier laminates, and reduces or eliminates manufacturing difficultieswithout detrimental economics.

[0011] It is a further object of the present invention to provide abeverage carton constructed of a laminate effective to prevent theintrusion of oxygen into the carton and therewith the oxygen degradationof flavor and vitamin components, particularly Vitamin C, and themigration, i.e., scalping, of flavor and aroma ingredients of thebeverage.

[0012] Another object of the invention is to provide a heat-sealablelaminate having a low oxygen permeability during filling over a range oftemperatures (cold fill to hot fill), at both room temperature andrefrigerated storage conditions and under both low and high humidityconditions.

SUMMARY OF THE INVENTION

[0013] In accordance with one embodiment of the present invention,improved heat-sealable non-foil laminates for fruit or citrus juices,punches, other beverages and the like providing an effective barrier tothe intrusion of oxygen and migration of flavors and for retention ofVitamin C, flavors and aromas are provided which comprise from thepaperboard surface to the inner surface which contacts the contents ofthe carton fabricated from the laminate, a paperboard substrate havingan interior and exterior surface, a first layer of polyolefin coated onthe exterior surface of the substrate, a first polyamide layer appliedonto the interior surface of the substrate, a first oxygen barrier layerof EVOH applied directly onto the first polyamide layer, a secondpolyamide layer applied directly onto said first EVOH layer, a first tielayer applied directly onto the polyamide layer, a second oxygen barrierlayer of EVOH applied directly onto the first tie layer, a second tielayer applied directly onto the second EVOH layer, and an innermostlayer of polyolefin that will contact the contents of the container.

[0014] In another embodiment of the invention, a laminate structure forpaperboard cartons or containers having the properties just describedcomprises paperboard which is coated with an outer layer of polyolefin,a first polyamide layer provided onto the inner surface of thepaperboard, a first layer of EVOH applied directly onto the firstpolyamide layer, a second polyamide layer applied directly onto thefirst EVOH layer, a first tie layer applied directly onto the secondpolyamide layer, a layer of polyolefin coated onto the first tie layer,a second tie layer applied onto the polyolefin layer, a second EVOHlayer coated onto the second tie layer, a third tie layer applieddirectly onto the second EVOH layer and an innermost layer of polyolefinapplied directly onto the third tie layer, the innermost layer ofpolyolefin serving as the contact layer with the contents of the carton.The ultimate structure of this embodiment in essentially the same asthat of the embodiment described above, but an extra tie and olefinlayer are included between the second polyamide and second EVOH layer.

[0015] The polyamide layers provide strength, heat resistance andmechanical toughness around the first EVOH oxygen barrier layer duringconversion of the laminate into the carton and during use. The secondEVOH layer which is incorporated into the laminate closer to the juice,punch or other beverage product contact surface, enhances the overalloxygen barrier properties while limiting flavor and aroma migration orscalping.

[0016] Cartons can be constructed easily from the laminates of thepresent invention and provide excellent gas-barrier protection forliquid and dry products and significant flavor retention and preventionof loss of Vitamin C from the juices and punches contained therein,resulting in extended shelf life for such products. Moreover, cartonblanks prepared from laminates of the present invention exhibit betterrunnability on equipment used for folding carton blanks compared tocarton blanks comprising laminates having a foil barrier layer, therebyfurther facilitating the manufacturing process.

BRIEF DESCRIPTION OF THE DRAWINGS

[0017]FIG. 1 is a schematic cross-sectional illustration showing abarrier-board laminate according to the invention.

[0018]FIG. 2 is a schematic cross-sectional illustration showing anotherform of barrier-board laminate according to the invention.

[0019]FIG. 3 is a graphic representation of % vitamin C retained vs.days after filling for cartons that were cold filled with orange juiceand stored at 38° F. for 64 days.

[0020]FIG. 4 is a graphic representation of % vitamin C retained vs.days after filling for cartons that were cold filled with orange juiceand stored at 73° F. for 64 days.

DETAILED DESCRIPTION

[0021] The laminate in FIG. 1 comprises a carrier layer or substrate 12of paperboard (100-300 lbs.*) onto which there is applied on one side anextrusion coating of polyolefin polymer layer 11 such as LDPE, HDPE,LLDPE, metallocene or the like, preferably LDPE, at a coating weight of9-20 lbs. and preferably about 12-15 lbs. to provide the outer surfaceof the laminate. Layer 11 is the outer “gloss” layer.

[0022] On the interior side of the substrate 12, there is applied afirst polyamide layer 13 at a coating weight of 1-15 lbs. and preferablyabout 5-10 lbs. The polyamide layer can be but is not limited to nylon6, nylon 66, nylon 10, nylon 6-10, nylon 12, amorphous nylons, MXD-6,nylon nanocomposites and other suitable polyamides. Onto the interiorsurface of the polyamide layer 13, there is applied a first oxygenbarrier layer of EVOH copolymer 14 having a coating weight of 1-10 lbs.and preferably 3-6 lbs. The EVOH copolymer may contain 26-44 mole %ethylene. Layer 14 can also be, but is not limited to, oxygen scavengingEVOH materials, EVOH nanocomposites, or blends of EVOH with polyolefinssuch as low density polyethylene. Layer 15 is a second layer ofpolyamide and is applied in an amount of 1-15 lbs. preferably about 5-10lbs. to the underside of the first EVOH layer. All of the materialslisted for layer 13 may also be used in layer 15.

[0023] A tie layer 16 is applied onto the inner side of the secondpolyamide layer 15 in an amount of 1-15 lbs. preferably 5-10 lbs. Thetie layer is preferably based on, but is not limited to, ethylene basedcopolymers modified with maleic anhydride functional groups such asPlexar and Bynel, but can also include other common tie resins such asNucrel, Primacor and Surlyn. Plexar 5125 is a preferred tie material.There is thereafter applied to the underside of the tie layer 16, alayer of polyolefin 17. The polyolefin 17 is applied in an amount of1-20 lbs., preferably about 4-10 lbs. The polyolefin is preferablypolyethylene and most preferably a low density polyethylene. A secondtie layer 18 is applied in an amount of 1-15 lbs. onto the underside ofthe polyolefin layer 17. A second oxygen barrier layer of EVOH 19 in anamount of 1-10 lbs. and preferably about 3-6 lbs. is applied onto thesecond tie layer 18. Layer 19 can be, but is not limited to, ethylenevinyl alcohol copolymers (containing 26-44 mole % ethylene), oxygenscavenging EVOH materials, EVOH nanocomposites, EVOH combined withinorganic fillers (such as talc or kaolin), or blends of EVOH with otherpolymers (such that EVOH remains the continuous phase); polyvinylalcohols (PVOH); polyamides such as, but not limited to, nylon 6, nylon66, nylon 6/9, nylon 10, nylon 6-10, nylon 11, nylon 12, amorphousnylons, MXD-6, nylon nanocomposites, nylon combined with inorganicfillers (such as talc or kaolin), and blends of nylon with otherpolymers (such that the nylon remains the continuous phase);polyethylene terephthalates including glycol-modified polyethyleneterephthalates, acid-modified polyethylene terephthalates, PETnanocomposites, PET combined with other inorganic fillers (such as talcor kaolin), and blends of PET with other polymers (such that the PETremains the continuous phase); PEN; vinylidene chloride copolymer;polyvinyl chloride polymers; polyolefins including, but not limited to,low density polyethylene, high density polyethylene, linear low densitypolyethylene, polypropylene, cyclic olefin copolymers, and blendsthereof; polycarbonates; and liquid crystal polymers. In addition,desiccants, molecular sieves, and the like may be added to layer 19 toimprove water vapor barrier characteristics of the layer; and molecularsieves, cyclodextrins, and the like may be added to same layer forimproved flavor/aroma barrier. A third tie layer 20 in an amount of 1-5lbs. is included between the second EVOH layer 19 and the innermostlayer of polyolefin 21 which is applied in an amount of 1-20 lbs. andpreferably about 4-10 lbs. The polyolefin layers 17 and 21 can be, butare not limited to, low density polyethylene, linear low densitypolyethylene, high density polyethylene, polypropylene, cyclic olefincopolymers, and blends thereof.

[0024] Looking at FIG. 2, another embodiment of the invention, thestructure has a paperboard substrate 32 (100-300 lbs.) onto one side ofwhich a coating of polyolefin 31 such as LDPE, HDPE, LLDPE, metallocene,or a blend thereof is applied in an amount of 9-20 lbs. and preferablyabout 12 lbs. Layer 31 is the “gloss” layer which contacts theatmosphere. A layer 33 of polyamide in a coating weight of between 1-15lbs. and preferably about 5-10 lbs. is applied onto the underside orinterior portion of the substrate 32. The polyamide layer can be but isnot limited to nylon 6, nylon 66, nylon 10, nylon 6-10, nylon 12,amorphous nylons, MXD-6, nylon nanocomposites and other suitablepolyamides. The underside or the interior of the polyamide layer 33 hasan EVOH layer 34 coated thereon of thickness 1-10 lbs. and preferablyabout 3-6 lbs. The EVOH layer can be but is not limited to EVOHcontaining 26-44 mole % ethylene, EVOH nanocomposites, oxygen scavengingEVOH, or blends of EVOH with polyolefins such as low densitypolyethylene. The EVOH layer 34 has another or second polyamide layer 35on its underside or interior, which has a coating weight of between 1-15lbs. and preferably about 5-10 lbs. All of the materials listed forlayer 33 may also be used in layer 35. A first tie layer 36 having acoating weight of 1-10 lbs., preferably about 4-7 lbs., is disposed onthe underside of the polyamide layer 35. A second EVOH layer 37 isapplied onto the underside of the first tie layer 36 and has a coatingweight of between 1-10 lbs., preferably 3-6 lbs. The second EVOH layercan be, but is not limited to, ethylene vinyl alcohol copolymers(containing 26-44 mole % ethylene), oxygen scavenging EVOH materials,EVOH nanocomposites, EVOH combined with inorganic fillers (such as talcor kaolin), or blends of EVOH with other polymers (such that EVOHremains the continuous phase); or blends of polyvinyl alcohols (PVOH);polyamides such as, but not limited to, nylon 6, nylon 66, nylon 6/9,nylon 10, nylon 6-10, nylon 11, nylon 12, amorphous nylons, MXD-6, nylonnanocomposites, nylon combined with inorganic fillers (such as talc orkaolin), and blends of nylon with other polymers (such that the nylonremains the continuous phase); polyethylene terephthalates includingglycol-modified polyethylene terephthalates, acid-modified polyethyleneterephthalates, PET nanocomposites, PET combined with other inorganicfillers (such as talc or kaolin), and blends of PET with other polymers(such that the PET remains the continuous phase); polyethylenenaphthalate PEN; vinylidene chloride copolymer; polyvinyl chloridepolymers; polyolefins including, but not limited to, low densitypolyethylene, high density polyethylene, linear low densitypolyethylene, polypropylene, cyclic olefin copolymers, and blendsthereof; polycarbonates; and liquid crystal polymers. In addition,desiccants, molecular sieves, and the like may be added to layer 37 toimprove water vapor barrier characteristics of the layer; and molecularsieves, cyclodextrins, and the like may be added to same layer forimproved flavor/aroma barrier. The second EVOH layer 37 has another orsecond tie layer 38 on its underside or interior, which has a coatingweight of between 1-10 lbs. and is preferably about 4-7 lbs. Finally, alayer of polyolefin polymer 39 such as low density polyethylene, linearlow density polyethylene, high density polyethylene, polypropylene,cyclic olefin copolymers, or a blend thereof, is disposed on the productside on the underside of the second tie layer 38. The product sidepolyolefin layer 39 has a coating weight of between 1-40 lbs. andpreferably 8-40 lbs.

[0025] The embodiment of FIG. 1 can be prepared as follows. First alayer of polyolefin 11 is extrusion coated on the outer surface of thesubstrate 12. There is then coextruded onto the inner surface of thesubstrate a four-layer sandwich of polyamide 13/EVOH 14/polyamide 15/tie16. A five-layer sandwich of polyolefin 17/tie 18/EVOH 19/tie20/polyolefin 21 is coextruded onto the inner surface of the four-layersandwich.

[0026] In the second embodiment of the invention shown in FIG. 2, alayer of polyolefin 31 is extrusion coated onto the paperboard substrate32 to provide the outer surface of the laminate. A three-layer sandwichof polyamide 33/EVOH 34/polyamide 35 is coextruded directly onto theinner surface of the paperboard substrate 32. A three-layer sandwich ofEVOH 37 surrounded by two tie layers 36 and 38 is coextruded onto thepolyamide layer 35 of the polyamide/EVOH/polyamide coextrusion. Finally,a product contact layer 39 of polyolefin is extruded onto the innersurface of tie layer 38 of that coextrusion.

[0027] Olefin polymers suitable for use in the present invention areheat-sealable and include polypropylene, high density polyethylene,medium density polyethylene, low density polyethylene, and linear lowdensity polyethylene and combinations thereof. Most preferred is lowdensity polyethylene. Any commercial extrusion coating grade polyolefinis suitable for use herein. The olefin polymers may include additives toprovide desired flow, adhesion or heat-sealing characteristics.

[0028] Paperboard for use in the present invention includes suitablyhigh grade paperboard stock, for example, milk carton stock. The boardmay have a basis weight of about 100 to 300 lbs./ream, preferably 150 toabout 200 lbs./ream. Either or both paperboard surfaces can be flame orcorona treated and/or primed to facilitate adhesion of subsequentpolymer layers. Primers which may be used include polyethylene imine(PEI) or ethylene vinyl acetate.

[0029] The nylon used in the present invention should be suitable forcoextrusion coating onto the paperboard substrate. Examples of nylonsfor use herein include polyamides or copolyamides such as nylon 6, nylon6,12 (the polycondensation product of hexamethylene diamine and a12-carbon dibasic acid); nylon 12 (the polymerization product of lauriclactam or cyclododecalactam, with 11 methylene units between the linking—NH—CO— groups in the polymer chain); nylon 11 (the polycondensationproduct of the monomer l-aminoundecanoic acid);; nylon 6,10(polyhexamethylene sebacamide) and amorphous nylons.

[0030] Tie layer resins suitable for coextruding with the nylon inaccordance with the invention include resins which have good adhesion toboth nylons and polyolefins. Preferred tie layer resins having suitableadhesion properties include anhydride-modified copolymers, especiallyanhydride modified ethylene copolymers. Most preferred are anhydridemodified linear low/low density ethylene copolymers. An anhydridemodified linear low/low density ethylene copolymer particularly suitablefor use as the tie layer material in the present invention is Bynel E388available from the duPont Corporation of America. Another duPontproduct, an anhydride modified ethylene acetate copolymer (Bynel E369)may also be used as the tie layer material. Other suitable tie layermaterials are those described in U.S. Pat. Nos. 4,087,587 and 4,087,588,both of which are incorporated herein by reference. Materials of thetype described therein are sold under the trade name Plexar.

[0031] The laminate of the invention produces an extended long life, lowoxygen permeable, leak free container laminate structure such as apaperboard based package or carton that prevents the transmission ofgases, in particular oxygen, therethrough, and in addition, prevents theescape of flavor components, or the ingress of microbiologicalcontaminates and further produces such a package that is economical on aper-package cost basis, is fundamentally compatible with existingconverting machinery, and can be formed, cold or hot filled, and sealedat economically high speeds using conventional packaging machinetemperatures, pressures and dwell times.

[0032] The following example is provided for further illustration of theinvention.

EXAMPLE 1

[0033] A non-foil barrier laminate consistent with the structure shownin FIG. 1 was produced using 5 lbs/ream nylon 6 in layer 13, 6 lbs/reamEVOH in layer 14, 5 lbs/ream nylon 6 in layer 15, and 3 lbs/ream EVOH inlayer 19. The laminate was compared to a laminate (Comparison Sample 1)as defined in FIG. 1 of application Ser. No. 10/288,841 of which theinstant application is a continuation in part comprising a paperboardsubstrate onto which there is applied a layer of low densitypolyethylene to provide the outer surface of the laminate, a polyamidepolymer applied onto the interior surface of the substrate, a layer ofethylene vinyl alcohol copolymer applied to the underside of thepolyamide polymer layer, a first tie layer applied to the underside ofthe ethylene vinyl alcohol copolymer layer, a polyolefin layer appliedto the underside of the first tie layer, a second tie layer applied ontothe polyolefin layer, a second layer of ethylene vinyl alcohol copolymerapplied to the underside of the second tie layer, a third tie layer isapplied to the underside of the second ethylene vinyl alcohol copolymerlayer, followed by a polyolefin polymer layer forming the productcontact surface and a laminate (Comparison Sample 2) described in KinseyU.S. Pat. No. 6,110,548 comprising a paperboard substrate having anouter layer of low density polyethylene, a layer of polyamide on theinterior side of the substrate, a tie layer applied on the underside ofthe polyamide layer, a first polyolefin polymer layer applied to theunderside of the tie layer, a second polyolefin polymer layer on theunderside of the first polyolefin polymer layer, a second tie layerdisposed on the underside of the second polyolefin polymer layer, anethylene vinyl alcohol copolymer layer disposed on the interior of thesecond tie layer, a third tie layer applied on the underside of theethylene vinyl alcohol copolymer layer and a final layer of polyolefinpolymer disposed on the underside of the third tie layer.

[0034] The skived liter gable top cartons were cold filled with fresh,not-from-concentrate orange juice and stored at refrigerated (38° F.)and ambient (73° F.) temperatures across a 64 day shelf life test.Vitamin C content of the juice was measured during filling andsubsequently at days 8, 21, 35, 51, and 64 after filling. Results forrefrigerated and ambient storage are shown in FIGS. 3 and 4,respectively. The packaging material of the present invention performscomparably to the Comparison Sample 1 material and better than theComparison Sample 2 structure at both storage conditions.

What is claimed is:
 1. A barrier laminate comprising a) a paperboardsubstrate having a first surface and a second surface, the secondsurface being opposite the first surface, b) a layer of polyolefinapplied directly onto the second surface of the paperboard substrate, c)a first polyamide layer applied directly on the first surface of thepaperboard substrate, d) a first oxygen barrier layer of EVOH applieddirectly onto the first polyamide layer, e) a second polyamide layerapplied directly onto the first oxygen barrier layer of EVOH, f) a firsttie layer applied directly on the second polyamide layer, g) a secondoxygen barrier layer selected from the group consisting of EVOH,polyvinyl alcohols, polyamides, polyesters, polyethylene terphthalates,polyolefins, cyclic olefin copolymers, polycarbonates, liquidcrystalline polymers and blends thereof and blends of any of theforegoing group members with at least one member selected from the groupconsisting of desiccants, molecular sieves and cyclodextrins applieddirectly on said first tie layer, h) a second tie layer applied directlyon said second oxygen barrier layer, and i) a polyolefin layer appliedonto said second tie layer as the innermost and product contact layer:2. A barrier laminate according to claim 1 wherein said polyolefin layerapplied onto the second surface of the paperboard substrate ispolyethylene.
 3. A barrier laminate according to claim 1 wherein saidpolyolefin applied onto the second tie layer and forming the productcontact layer is polyethylene.
 4. A barrier laminate according to claim1 wherein said first and second polyamide layers each comprise a memberselected from the group consisting of nylon 6, nylon 66, nylon 10, nylon6-10, nylon 11, nylon 12, amorphous nylons, MXD-6 and nylonnanocomposites.
 5. A barrier laminate according to claim 1 wherein thesecond oxygen barrier layer is EVOH.
 6. A barrier laminate according toclaim 1 wherein the tie layers are each an ethylene based copolymermodified with maleic anhydride functional groups.
 7. A barrier laminateaccording to claim 6 wherein the tie layers are each Plexar.
 8. Abarrier laminate according to claim 5 wherein the EVOH contains 26-44mol % ethylene.
 9. A barrier laminate according to claim 1 wherein thesecond oxygen barrier layer is separated from the first tie layer by alayer of polyolefin coated directly on the first tie layer and a thirdtie layer coated directly on the polyolefin layer.
 10. A high oxygenbarrier laminate comprising a) a paperboard substrate having a firstsurface and a second surface, the second surface being opposite thefirst surface, b) a layer of polyolefin applied directly onto the secondsurface of the paperboard substrate, c) a first polyamide layer applieddirectly on the first surface of the paperboard substrate, d) a firstoxygen barrier layer of EVOH applied directly onto the first polyamidelayer, e) a second polyamide layer applied directly onto the firstoxygen barrier layer of EVOH, f) a first tie layer applied directly onthe second polyamide layer, g) a layer of polyolefin applied directlyonto said first tie layer, h) a second tie layer applied directly ontosaid polyolefin layer. i) a second oxygen barrier layer selected fromthe group consisting of EVOH, polyvinyl alcohols, polyamides,polyesters, polyethylene terphthalates, polyolefins, cyclic olefincopolymers, polycarbonates, liquid crystalline polymers and blendsthereof and blends of any of the foregoing group members with at leastone member selected from the group consisting of desiccants, molecularsieves and cyclodextrins applied directly on said first tie layer, j) athird tie layer applied directly on said second oxygen barrier layer,and k) a polyolefin layer applied onto said third tie layer as theinnermost and product contact layer.
 12. A high oxygen barrier laminateaccording to claim 11 wherein the second oxygen barrier layer comprisesEVOH.
 13. A method for extending the shelf life of a beverage includingfruit and citrus juices stored in a paperboard container wherein saidcontainer is formed from a laminate according to claim
 1. 14. A methodfor extending the shelf life of a beverage including fruit and citrusjuices stored in a paperboard container wherein said container is formedfrom a laminate according to claim
 11. 15. A sealed container and aperishable product contained therein, the container being constructed ofa laminate according to claim 1, the product being hot filled into thecontainer, said product having been heated to a temperature sufficientto kill essentially all of the micro organisms in the food product,sealing the container and cooling the product within the container toensure that the product is shelf stable.
 16. A sealed container and aperishable product contained therein, the container being constructed ofa laminate according to claim 11, the product being hot filled into thecontainer, said product having been heated to a temperature sufficientto kill essentially all of the micro organisms in the food product,sealing the container and cooling the product within the container toensure that the product is shelf stable.
 17. A sealed container and aperishable product contained therein constructed of a laminate accordingto claim 11, the product being cold filled into the container.
 18. Acontainer blank constructed from a laminate according to claim
 1. 19. Acontainer blank constructed from a laminate according to claim
 11. 20. Acontainer blank constructed from a laminate according to claim
 12. 21. Alaminated packaging material especially for heat sealable, hot fill,room temperature storage of liquid food products comprising a barrierlaminate according to claim
 1. 22. A laminated packaging materialespecially for heat sealable, hot fill, room temperature storage ofliquid food products comprising a barrier laminate according to claim11.
 23. A laminated packaging material especially for heat sealable,cold fill, room temperature storage of liquid food products comprising abarrier laminate according to claim
 1. 24. A laminated packagingmaterial especially for heat sealable, cold fill, room temperaturestorage of liquid food products comprising a barrier laminate accordingto claim
 11. 25. A method for extending the shelf life of a beverageincluding fruit and citrus juices stored in a paperboard containercomprising a barrier laminate according to claim
 1. 26. A method forextending the shelf life of a beverage including fruit and citrus juicesstored in a paperboard container comprising a barrier laminate accordingto claim 11.